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WO2011161419A1 - Compositions de transfert thermique - Google Patents

Compositions de transfert thermique Download PDF

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Publication number
WO2011161419A1
WO2011161419A1 PCT/GB2011/000952 GB2011000952W WO2011161419A1 WO 2011161419 A1 WO2011161419 A1 WO 2011161419A1 GB 2011000952 W GB2011000952 W GB 2011000952W WO 2011161419 A1 WO2011161419 A1 WO 2011161419A1
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WO
WIPO (PCT)
Prior art keywords
composition
weight
heat transfer
composition according
performance data
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2011/000952
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English (en)
Inventor
Robert Elliott Low
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Orbia Advance Corp SAB de CV
Original Assignee
Mexichem Amanco Holding SA de CV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=42582988&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2011161419(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to KR1020137002172A priority Critical patent/KR101349716B1/ko
Priority to US13/701,328 priority patent/US20130193369A1/en
Priority to EP23192441.6A priority patent/EP4253501A3/fr
Priority to ES11738255.6T priority patent/ES2545186T3/es
Priority to RU2013103360/05A priority patent/RU2567950C2/ru
Priority to EP15169704.2A priority patent/EP2930222B1/fr
Priority to CA2800762A priority patent/CA2800762A1/fr
Priority to AU2011268772A priority patent/AU2011268772B2/en
Priority to CN2011800309611A priority patent/CN102959036A/zh
Application filed by Mexichem Amanco Holding SA de CV filed Critical Mexichem Amanco Holding SA de CV
Priority to BR112012030454A priority patent/BR112012030454A2/pt
Priority to MX2012013767A priority patent/MX2012013767A/es
Priority to PL11738255T priority patent/PL2609168T3/pl
Priority to EP11738255.6A priority patent/EP2609168B1/fr
Publication of WO2011161419A1 publication Critical patent/WO2011161419A1/fr
Anticipated expiration legal-status Critical
Priority to US14/851,030 priority patent/US10266736B2/en
Priority to US16/391,554 priority patent/US10844260B2/en
Priority to US17/094,434 priority patent/US11760911B2/en
Priority to US18/456,665 priority patent/US20230416582A1/en
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5018—Halogenated solvents
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03C—POSITIVE-DISPLACEMENT ENGINES DRIVEN BY LIQUIDS
    • F03C99/00—Subject matter not provided for in other groups of this subclass
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
    • G06Q30/00—Commerce
    • G06Q30/018—Certifying business or products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/20—Ternary blends of expanding agents
    • C08J2203/202—Ternary blends of expanding agents of physical blowing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
    • Y02A40/963—Off-grid food refrigeration
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49716—Converting

Definitions

  • the invention relates to heat transfer compositions, and in particular to heat transfer compositions which may be suitable as replacements for existing refrigerants such as R- 134a, R-152a, R-1234yf, R-22, R-410A, R-407A, R-407B, R-407C, R507 and R-404a.
  • the properties preferred in a refrigerant include low toxicity, non-flammability, non-corrosivity, high stability and freedom from objectionable odour.
  • Other desirable properties are ready compressibility at pressures below 25 bars, low discharge temperature on compression, high refrigeration capacity, high efficiency (high coefficient of performance) and an evaporator pressure in excess of 1 bar at the desired evaporation temperature.
  • Dichlorodifluoromethane (refrigerant R-12) possesses a suitable combination of properties and was for many years the most widely used refrigerant. Due to international concern that fully and partially halogenated chlorofluorocarbons were damaging the earth's protective ozone layer, there was general agreement that their manufacture and use should be severely restricted and eventually phased out completely. The use of dichlorodifluoromethane was phased out in the 1990's.
  • Chlorodifluoromethane (R-22) was introduced as a replacement for R- 2 because of its lower ozone depletion potential. Following concerns that R-22 is a potent greenhouse gas, its use is also being phased out.
  • R- 10A and R-407 refrigerants have been introduced as a replacement refrigerant for R-22.
  • R-22, R-410A and the R-407 refrigerants all have a high global warming potential (GWP, also known as greenhouse warming potential).
  • GWP global warming potential
  • R-134a 1 ,1,1,2-tetrafluoroethane
  • R-152a (1 ,1-difluoroethane) has been identified as an alternative to R-134a. It is somewhat more efficient than R-134a and has a greenhouse warming potential of 120. However the flammability of R-152a is judged too high, for example to permit its safe use in mobile air conditioning systems. In particular it is believed that its lower flammable limit in air is too low, its flame speeds are too high, and its ignition energy is too low.
  • R-1234yf (2,3,3,3-tetrafluoropropene) has been identified as a candidate alternative refrigerant to replace R-134a in certain applications, notably the mobile air conditioning or heat pumping applications. Its GWP is about 4. R-1234yf is flammable but its flammability characteristics are generally regarded as acceptable for some applications including mobile air conditioning or heat pumping. In particular, when compared with R-152a, its lower flammable limit is higher, its minimum ignition energy is higher and the flame speed in air is significantly lower than that of R-152a.
  • R-1234yf The energy efficiency and refrigeration capacity of R-1234yf have been found to be significantly lower than those of R-134a and in addition the fluid has been found to exhibit increased pressure drop in system pipework and heat exchangers. A consequence of this is that to use R-1234yf and achieve energy efficiency and cooling performance equivalent to R-134a, increased complexity of equipment and increased size of pipework is required, leading to an increase in indirect emissions associated with equipment. Furthermore, the production of R-1234yf is thought to be more complex and less efficient in its use of raw materials (fluorinated and chlorinated) than R-134a. So the adoption of R-I234yf to replace R-134a will consume more raw materials and result in more indirect emissions of greenhouse gases than does R-1 4a. Some existing technologies designed for R-134a may not be able to accept even the reduced flammability of some heat transfer compositions (any composition having a GWP of less than 150 is believed to be flammable to some extent).
  • a principal object of the present invention is therefore to provide a heat transfer composition which is usable in its own right or suitable as a replacement for existing refrigeration usages which should have a reduced GWP, yet have a capacity and energy efficiency (which may be conveniently expressed as the "Coefficient of Performance") ideally within 10% of the values, for example of those attained using existing refrigerants (e.g. R-134a, R-152a, R-1234yf, R-22, R-410A, R-407A, R- 07B, R-407C, R507 and R- 404a), and preferably within less than 10% (e.g. about 5%) of these values. It is known in the art that differences of this order between fluids are usually resolvable by redesign of equipment and system operational features.
  • the composition should also ideally have reduced toxicity and acceptable flammability.
  • the subject invention addresses the above deficiencies by the provision of a heat transfer composition
  • a heat transfer composition comprising:
  • a second component selected from difluoromethane (R-32), propene (R-1270), propane (R290) and mixtures thereof;
  • a third component selected from pentafluoroethane (R-125), 1 ,1 ,1 ,2- tetrafluoroethane (R-134a), and mixtures thereof; and optionally
  • compositions of the invention unless otherwise stated.
  • compositions of the invention comprise up to about 60 or 70 % by weight R- l234ze(E), such as from about 5 to about 50 %, for example from about 0 to about 40 %.
  • compositions of the invention comprise up to about 50 % by weight of the second component, such as from about 10 to about 40 %, for example from about 15 to about 35 %.
  • compositions of the invention contain from about 10 to about 80 % by weight of the third component, preferably from about 15 to about 70 %, such as from about 20 to about 60 %.
  • compositions of the invention comprise from about 0 to about 15 % (e.g. about 5 to about 15 %) by weight of the fourth component.
  • compositions of the invention comprise from about 5 to about 60 % by weight of the fourth component.
  • compositions herein are by weight based on the total weight of the compositions, unless otherwise stated.
  • the components and the amounts of the components of the compositions of the invention typically are chosen such that the flammability of both liquid and vapour phases is reduced relative to the pure flammable component, or rendered completely non-flammable.
  • the second component is R-32.
  • the third component comprises a mixture of R-125 and R-134a.
  • compositions of the invention comprise R-1234ze(E), R-32, R-125 and R- 34a.
  • An advantageous composition of the invention comprises from about 5 to about 40 % by weight of R-1234ze(E), from about 20 to about 35 % by weight R-32, from about 15 to about 30 % by weight R-125, and from about 12 to about 50 % by weight R-134a.
  • compositions of the invention contain from about 10 to about 50 % by weight R-1234ze(E), from about 22 to about 40 % by weight R-32, from about 10 to about 30 % by weight R-125, and from about 15 to about 30 % by weight R-134a.
  • a preferred group of compositions of the invention contain from about 17 to about 46 % by weight R-1234ze(E), from about 26 to about 40 % by weight R-32, from about 10 to about 18 % by weight R-125, and from about 15 to about 30 % by weight R-134a.
  • compositions of the invention contain from about 14 to about 40 % by weight R-1234ze(E), from about 22 to about 38 % by weight R-32, from about 18 to about 28 % by weight R-125, and from about 15 to about 30 % by weight R-134a.
  • a preferred composition of the invention consists essentially of about 20 % by weight R- 1234ze(E), about 30 % by weight R-32, about 25 % by weight R-125, and about 25 % by weight R-134a.
  • the invention excludes compositions that comprise or consist of approximately 1 to 16 % by weight (e.g. approximately 3 to 8 %) R-1234ze, approximately 8 to 20 % by weight R-32 (e.g. approximately 12 to 18 %), approximately 8 to 20 % by weight R-125 (e.g. approximately 8 to 12 %) and approximately 60 to 72 % by weight R- 134a (e.g. about 70 to 75 %).
  • the invention excludes compositions that comprise or consist of approximately 6 % by weight R-1234ze, approximately 14 % by weight R-32, approximately 14 % by weight R-125 and approximately 66 % by weight R-134a.
  • compositions of the invention contain R-161 as a fourth component.
  • the R-161 is present in such compositions in an amount of from about 0 to about 60 % by weight. In a preferred aspect, the R-161 is present in an amount of from 10 to about 30 % by weight, for example from about 10 to about 20 % by weight.
  • a preferred composition of the invention comprises R-1234ze(E), R-32, R-161 and R- 134a.
  • An advantageous composition of the invention comprises from about 5 to about 60 % by weight R-1234ze(E), from about 20 to about 50 % by weight R-32, from about 10 to about 60 % by weight R-161 , and from about 10 to about 40 % by weight R-134a.
  • a preferred composition of the invention of comprises from about 10 to about 60 % by weight R-123 ze(E), from about 20 to about 50 % by weight R-32, from about 10 to about 40 % by weight R-161, and from about 10 to about 30 % by weight R-134a.
  • a further preferred composition of the invention comprises from about 30 to about 60 % by weight R-1234ze(E), from about 20 to about 50 % by weight R-32, from about 10 to about 30 % by weight R-161 , and from about 10 to about 25 % by weight R-134a.
  • Another advantageous composition of the invention comprises from about 40 to about 60 % by weight R-1234ze(E), from about 20 to about 50 % by weight R-32, from about 10 to about 20 % by weight R-161 , and from about 10 to about 25 % by weight R-134a.
  • a preferred composition of the invention comprises R-1234ze(E), R-32, R-161 and R-125.
  • An advantageous composition of the invention comprises from about 5 to about 70 % by weight R-1234ze(E), from about 15 to about 50 % by weight R-32, from about 10 to about 40 % by weight R-161, and from about 10 to about 40 % by weight R-125.
  • a preferred composition of the invention comprises from about 10 to about 65 % by weight R-1234ze(E), from about 16 to about 40 % by weight R-32, from about 10 to about 30 % by weight R-161 , and from about 10 to about 25 % by weight R-125.
  • a further preferred composition of the invention comprises from about 25 to about 60 % by weight R-1234ze(E), from about 20 to about 40 % by weight R-32, from about 10 to about 20 % by weight R-161 , and from about 10 to about 25 % by weight R-125.
  • composition of the invention comprises from about 20 to about 55 % by weight R-1234ze(E), from about 16 to about 35 % by weight R-32, from about 20 to about 30 % by weight R-161 , and from about 10 to about 25 % by weight R-125.
  • compositions of the invention consist essentially of any of the stated components, in any of the stated amounts.
  • compositions of the invention contain substantially no other components, particularly no further (hydro)(fluoro)compounds (e.g. (hydro)(fIuoro)alkanes or (hydro)(fluoro)alkenes) known to be used in heat transfer compositions.
  • hydro)(fluoro)compounds e.g. (hydro)(fIuoro)alkanes or (hydro)(fluoro)alkenes
  • any of the compositions of the invention described herein, including those with specifically defined amounts of components, may consist essentially of (or consist of) the components defined in those compositions.
  • compositions according to the invention conveniently comprise substantially no R-1225 (pentafluoropropene), conveniently substantially no R-1225ye (1 ,2,3,3,3- pentafluoropropene) or R-1225zc (1 ,1 ,3,3,3-pentafluoropropene), which compounds may have associated toxicity issues.
  • compositions of the invention contain 0.5% by weight or less of the stated component, preferably 0.1% or less, based on the total weight of the composition.
  • compositions of the invention may contain substantially no:
  • compositions of the invention have zero ozone depletion potential.
  • compositions of the invention deliver acceptable properties for use in air conditioning, heat pump and low and medium temperature refrigeration systems as alternatives to existing refrigerants such as R-22, R-410A, R- 407A, R-407B, R-407C, R507 and R-404a, while reducing GWP and without resulting in high flammability hazard.
  • low temperature refrigeration means refrigeration having an evaporation temperature of from about -50 to about -20 °C.
  • Medium temperature refrigeration means refrigeration having an evaporation temperature of from about -20 to about 0 °C.
  • IPCC Intergovernmental Panel on climate Change
  • TAR Tin Assessment Report
  • the compositions of the invention have a GWP less than R-22, R-410A, R-407A, R-407B, R-407C, R507 or R-404a.
  • the GWP of the compositions of the invention is less than about 2800
  • the GWP may be less than 2800, 2500, 2300, 2100, 2000, 1900, 1800, 1700, 1500 or 1400.
  • compositions of the invention have a GWP that is less than 1500, preferably less than 1400, more preferably less than 1300, 000, 900 or 700 or 500.
  • compositions are of reduced flammability hazard when compared to the individual flammable components of the compositions, e.g. R-32, propene or propane.
  • the compositions have one or more of (a) a higher lower flammable limit; (b) a higher ignition energy; or (c) a lower flame velocity compared to R-32, propene, propane or R-1234yf.
  • the compositions of the invention are nonflammable (or inflammable).
  • Flammability may be determined in accordance with ASHRAE Standard 34 incorporating the ASTM Standard E-681 with test methodology as per Addendum 34p dated 2004, the entire content of which is incorporated herein by reference.
  • Temperature glide which can be thought of as the difference between bubble point and dew point temperatures of a zeotropic (non-azeotropic) mixture at constant pressure, is a characteristic of a refrigerant; if it is desired to replace a fluid with a mixture then it is often preferable to have similar or reduced glide in the alternative fluid.
  • the compositions of the invention are zeotropic.
  • the temperature glide (in the evaporator) of the compositions of the invention is less than about 10K, preferably less than about 5K.
  • the volumetric refrigeration capacity of the compositions of the invention is at least 85% of the existing refrigerant fluid it is replacing, preferably at least 90% or even at least 95%.
  • compositions of the invention typically have a volumetric refrigeration capacity that is at least 90% of that of R-407C in medium temperature and/or low temperature application
  • the compositions of the invention have a volumetric refrigeration capacity that is at least 95% of that of R-407C, for example from about 95% to about 120% of that of R- 1234yf.
  • the cycle efficiency (Coefficient of Performance, COP) of the compositions of the invention is within about 5% or even better than the existing refrigerant fluid it is replacing
  • the compressor discharge temperature of the compositions of the invention is within about 15K of the existing refrigerant fluid it is replacing, preferably about 10K or even about 5K.
  • compositions of the invention preferably have energy efficiency at least 95% (preferably at least 98%) of R-407C, R-407A or R-404A under equivalent conditions, while having reduced or equivalent pressure drop characteristic and cooling capacity at 95% or higher of R-407C, R-407A or R-404A values.
  • the compositions have higher energy efficiency and lower pressure drop characteristics than R-407C, R-407A or R-404A under equivalent conditions.
  • the compositions also advantageously have better energy efficiency and pressure drop characteristics than R-407C, R-407A or R-404A alone.
  • the heat transfer compositions of the invention are suitable for use in existing designs of equipment, and are compatible with all classes of lubricant currently used with established HFC refrigerants. They may be optionally stabilized or compatibilized with mineral oils by the use of appropriate additives.
  • the composition of the invention when used in heat transfer equipment, is combined with a lubricant.
  • the lubricant is selected from the group consisting of mineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (alpha-olefins) and combinations thereof.
  • PABs polyalkyl benzenes
  • POEs polyol esters
  • PAGs polyalkylene glycols
  • PAG esters polyalkylene glycol esters
  • PVEs polyvinyl ethers
  • poly (alpha-olefins) poly (alpha-olefins) and combinations thereof.
  • the lubricant further comprises a stabiliser.
  • the stabiliser is selected from the group consisting of diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.
  • composition of the invention may be combined with a flame retardant.
  • the additional flame retardant is selected from the group consisting of tri- (2-chloroethyl)-phosphate, (chloropropyl) phosphate, tri-(2,3-dibromopropyl)-phosphate, tri- (1 ,3-dichloropropyl)-phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminium trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated bromocarbon, trifluoro iodomethane, perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.
  • the heat transfer composition is a refrigerant composition.
  • the invention provides a heat transfer device comprising a composition of the invention.
  • the heat transfer device is a refrigeration device.
  • the heat transfer device is selected from group consisting of automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, residential refrigerator systems, residential freezer systems, commercial refrigerator systems, commercial freezer systems, chiller air conditioning systems, chiller refrigeration systems, and commercial or residential heat pump systems.
  • the heat transfer device is a refrigeration device or an air-conditioning system.
  • the heat transfer device contains a centrifugal-type compressor.
  • the invention also provides the use of a composition of the invention in a heat transfer device as herein described.
  • a blowing agent comprising a composition of the invention.
  • a foamable composition comprising one or more components capable of forming foam and a composition of the invention.
  • the one or more components capable of forming foam are selected from polyurethanes, thermoplastic polymers and resins, such as polystyrene, and epoxy resins.
  • a foam obtainable from the foamable composition of the invention.
  • the foam comprises a composition of the invention.
  • a sprayable composition comprising a material to be sprayed and a propellant comprising a composition of the invention.
  • a method for cooling an article which comprises condensing a composition of the invention and thereafter evaporating said composition in the vicinity of the article to be cooled.
  • a method for heating an article which comprises condensing a composition of the invention in the vicinity of the article to be heated and thereafter evaporating said composition.
  • a method for extracting a substance from biomass comprising contacting the biomass with a solvent comprising a composition of the invention, and separating the substance from the solvent.
  • a method of cleaning an article comprising contacting the article with a solvent comprising a composition of the invention.
  • a method for extracting a material from an aqueous solution comprising contacting the aqueous solution with a solvent comprising a composition of the invention, and separating the material from the solvent.
  • a method for extracting a material from a particulate solid matrix comprising contacting the particulate solid matrix with a solvent comprising a composition of the invention, and separating the material from the solvent.
  • a mechanical power generation device containing a composition of the invention.
  • the mechanical power generation device is adapted to use a Rankine Cycle or modification thereof to generate work from heat.
  • a method of retrofitting a heat transfer device comprising the step of removing an existing heat transfer fluid, and introducing a composition of the invention.
  • the heat transfer device is a refrigeration device or (a static) air conditioning system.
  • the method further comprises the step of obtaining an allocation of greenhouse gas (e.g. carbon dioxide) emission credit.
  • greenhouse gas e.g. carbon dioxide
  • an existing heat transfer fluid can be fully removed from the heat transfer device before introducing a composition of the invention.
  • An existing heat transfer fluid can also be partially removed from a heat transfer device, followed by introducing a composition of the invention.
  • the existing heat transfer fluid is R-134a
  • the composition of the invention contains R134a, R-1234ze(E), the second component, optionally R-125, and optionally the fourth component (and optional components such as a lubricant, a stabiliser or an additional flame retardant), R-1234ze(E), the second component, any R-125 and/or the fourth component can be added to the R-134a in the heat transfer device, thereby forming the compositions of the invention, and the heat transfer device of the invention, in situ.
  • Some of the existing R-134a may be removed from the heat transfer device prior to adding the R-1234ze(E), the second component, etc, to facilitate providing the components of the compositions of the invention in the desired proportions.
  • the invention provides a method for preparing a composition and/or heat transfer device of the invention comprising introducing R-1234ze(E), a second component selected from R-32, propene and propane, optionally R-125, and optionally a fourth component selected from R-161, R-152a and mixtures thereof, and optional components such as a lubricant, a stabiliser or an additional flame retardant, into a heat transfer device containing an existing heat transfer fluid which is R-134a.
  • R-134a is removed from the heat transfer device before introducing the R-1234ze(E), the second component, etc.
  • compositions of the invention may also be prepared simply by mixing the R- 1234ze(E), the second and third components, and optionally the fourth component (and optional components such as a lubricant, a stabiliser or an additional flame retardant) in the desired proportions.
  • the compositions can then be added to a heat transfer device (or used in any other way as defined herein) that does not contain R-134a or any other existing heat transfer fluid, such as a device from which R-134a or any other existing heat transfer fluid have been removed.
  • a method for reducing the environmental impact arising from operation of a product comprising an existing compound or composition comprising replacing at least partially the existing compound or composition with a composition of the invention.
  • this method comprises the step of obtaining an allocation of greenhouse gas emission credit.
  • this environmental impact can be considered as including not only those emissions of compounds or compositions having a significant environmental impact from leakage or other losses, but also including the emission of carbon dioxide arising from the energy consumed by the device over its working life.
  • Such environmental impact may be quantified by the measure known as Total Equivalent Warming Impact (TEWI). This measure has been used in quantification of the environmental impact of certain stationary refrigeration and air conditioning equipment, including for example supermarket refrigeration systems (see, for example, http://en.wikipedia.orq/wiki T otal equivalent warming impact).
  • the environmental impact may further be considered as including the emissions of greenhouse gases arising from the synthesis and manufacture of the compounds or compositions.
  • the manufacturing emissions are added to the energy consumption and direct loss effects to yield the measure known as Life-Cycle Carbon Production (LCCP, see for example http://www.sae.org/events/aars/presentations/2007papasawa.pdf).
  • LCCP Life-Cycle Carbon Production
  • the use of LCCP is common in assessing environmental impact of automotive air conditioning systems.
  • a method for generating greenhouse gas emission credit(s) comprising (i) replacing an existing compound or composition with a composition of the invention, wherein the composition of the invention has a lower GWP than the existing compound or composition; and (ii) obtaining greenhouse gas emission credit for said replacing step.
  • the use of the composition of the invention results in the equipment having a lower Total Equivalent Warming Impact, and/or a lower Life-Cycle Carbon Production than that which would be attained by use of the existing compound or composition.
  • these methods may be carried out on any suitable product, for example in the fields of air- conditioning, refrigeration (e.g. low and medium temperature refrigeration), heat transfer, blowing agents, aerosofs or sprayable propellents, gaseous dielectrics, cryosurgery, veterinary procedures, dental procedures, fire extinguishing, flame suppression, solvents (e.g. carriers for flavorings and fragrances), cleaners, air horns, pellet guns, topical anesthetics, and expansion applications.
  • refrigeration e.g. low and medium temperature refrigeration
  • blowing agents e.g. low and medium temperature refrigeration
  • aerosofs or sprayable propellents gaseous dielectrics
  • cryosurgery e.g., veterinary procedures, dental procedures, fire extinguishing, flame suppression, solvents (e.g. carriers for flavorings and fragrances), cleaners, air horns, pellet guns, topical anesthetics, and expansion applications.
  • the field is air-conditioning or refrigeration.
  • suitable products include a heat transfer devices, blowing agents, foamable compositions, sprayable compositions, solvents and mechanical power generation devices.
  • the product is a heat transfer device, such as a refrigeration device or an air-conditioning unit.
  • the existing compound or composition has an environmental impact as measured by GWP and/or TEWI and/or LCCP that is higher than the composition of the invention which replaces it.
  • the existing compound or composition may comprise a fluorocarbon compound, such as a perfluoro-, hydrofluoro-, chlorofluoro- or hydrochlorofluoro-carbon compound or it may comprise a fluorinated olefin
  • the existing compound or composition is a heat transfer compound or composition such as a refrigerant.
  • refrigerants that may be replaced include R-134a, R-152a, R-I234yf, R-410A, R-407A, R-407B, R-407C, R-407D, R-407F, R507, R- 22 and R-404A.
  • the compositions of the invention are particularly suited as replacements for R-22, R-404A, R-407A, R-407B, R-407C or R-410A.
  • any amount of the existing compound or composition may be replaced so as to reduce the environmental impact. This may depend on the environmental impact of the existing compound or composition being replaced and the environmental impact of the replacement composition of the invention. Preferably, the existing compound or composition in the product is fully replaced by the composition of the invention.
  • the invention is illustrated by the following non-limiting examples.
  • Blend A The performance of Blend A is shown in Tables 1 and 2 with the estimated performance of the commercially available and commonly used refrigerants R-407C, R-407A and R-404A indicated for comparison.
  • the capacity, energy efficiency (as Coefficient of Performance) and suction line pressure drop are compared to a baseline of R-407C, as this refrigerant has the highest theoretical COP and lowest direct GWP of the established refrigerants.
  • this composition has comparable energy efficiency than R-407C, better cooling capacity than R-407C, lower pressure drop and essentially comparable discharge temperature. Furthermore the capacity and energy efficiency of the composition is superior to R-404A.
  • the composition has lower GWP than R-407C and so the total environmental warming impact (TEWI) of a system using this fluid will be lower than that achievable using R-407C or R-404A.
  • the fluid further exhibits close match of performance parameters to R-407A, which is today finding increasing utility as a refrigerant to replace R-404A.
  • the operating pressures are very similar to those found with R-407A, so replacement of R-407A with this composition would require little or no change to a refrigeration system control scheme.
  • composition is believed to be essentially non-flammable.
  • compositions of the invention comprising: R-32 in range 20-35% w w; R-125 in range 15-30% w/w; R-134a in range 15-50% w w and R- 1234ze being the balance, using the same conditions as in Table 1 and with R-407C as the reference fluid for comparison of capacity, energy efficiency and suction line pressure drop.
  • the compositions of the invention give acceptable or improved performance with lower GWP and lower overall TEWI than R-407A, R-407C or R-404A.
  • Example 3 The performance was modelled for further compositions of the invention as explained in more detail below.
  • the derivation of the model used is as follows.
  • R-1234ze(E) required to model refrigeration cycle performance, namely critical point, vapour pressure, liquid and vapour enthalpy, liquid and vapour density and heat capacities of vapour and liquid were accurately determined by experimental methods over the pressure range 0-200 bar and temperature range -40 to 200 °C, and the resulting data used to generate Helmholtz free energy equation of state models of the Span-Wagner type for the fluid in the NIST REFPROP Version 8.0 software, which is more fully described in the user guide www.nist.qov/srd/PDFfiles/REFPROP8.PDF, and is incorporated herein by reference.
  • the vapour liquid equilibrium behaviour of R-1234ze(E) was studied in a series of binary pairs with carbon dioxide, R-32, R-125, R-134a, R-152a, R-161, propane and propylene over the temperature range -40 to +60°C, which encompasses the practical operating range of most refrigeration and air conditioning systems.
  • the composition was varied over the full compositional space for each binary in the experimental programme, mixture parameters for each binary pair were regressed to the experimentally obtained data and the parameters were also incorporated into the REFPROP software model.
  • the academic literature was next searched for data on the vapour liquid equilibrium behaviour of carbon dioxide with the hydrofluorocarbons R-32, R-125, R-152a, R-161 and R-152a.
  • VLE data obtained from sources were then used to generate mixing parameters for the relevant binary mixtures and these were then also incorporated into the REFPROP model.
  • the standard REFPROP mixing parameters for carbon dioxide with propane and propylene were also incorporated to this model.
  • the resulting software model was used to compare the performance of selected fluids of the invention with R-407A in a low temperature supermarket refrigeration cycle simulation.
  • the use of liquid injection to control compressor discharge temperature was included as a feature of this cycle. Liquid injection is recommended by compressor manufacturers and refrigerant suppliers if R-407A or R-22 is to be used in such applications.
  • the quantity of liquid required to maintain the compressor discharge gas at or below the desired maximum temperature was estimated by assuming that the liquid to be injected to the compressor was at the same thermodynamic state as the liquid leaving the condenser and by then performing a heat balance on the machine.
  • the total compression work required was then derived from knowledge of the total mass flow through the compressor and the specified outlet and inlet refrigerant states.
  • the comparison of fluids was carried out assuming equivalent mean evaporating and condensing temperatures for the refrigerants, and fixed degrees of subcooling and evaporator superheat. Fixed pressure drops were assumed for R-407A in the evaporator, condenser and compressor suction gas line. The pressure drops for the fluids of the invention were then estimated for the same cycle by estimating the achieved compressor throughput with the fluid, deriving the mass flowrate of the refrigerant in the line and then calculating the pressure drop by comparison with the assumed pressure drop for the reference refrigerant.
  • the compressor was assumed to be a piston type machine running at fixed speed and known piston displacement with an effective clearance volume ratio of 3% and an average adiabatic (isentropic) efficiency of 65%, operating at a constant compressor suction gas temperature of 20°C.
  • the volumetric efficiency of the compressor was then estimated for each refrigerant from the pressure ratio developed over the compressor and the thermodynamic properties of the gas using the standard relationship for estimation of volumetric efficiency in such a machine.
  • compositions of the invention containing 16 to 40 % by weight R-32, 10 to 24 % by weight R-125, 16 to 28 % by weight R-134a and 8 to 56 % by weight R-1234ze(E) is shown in Tables 3 to 34 below.
  • the fluids of the invention offer highly unexpected significant improved environmental performance when compared to comparable known HFC refrigerants (e.g. R-407A, R407F and R-404a) on the grounds of:
  • the currently most preferred fluids of the invention are those whose cooling capacity matches that of R-404A, whose condensing pressure is lower than that of R-404A and whose energy efficiency is higher than that of R-407A or R-407F when compared in this manner.
  • compositions of the invention it has also been found possible with the compositions of the invention to exceed the performance of R-407D, a fluid which is used for certain refrigerated transport applications as an alternative to the CFC refrigerant R-500, for example if R-32 content in the range 16- 20% is used. It is evident from the performance comparison that the capacity and COP of R-407D can be matched or bettered whilst maintaining compressor discharge pressure at or below that of R-407D. Thus the previously claimed benefits of the fluids are also achieved for this application.
  • the Coefficient of Performance (COP) of the fluids is not only higher than that of R-407A in the equivalent cycle conditions but is higher than that achievable with the R32/R125/R134a/R1234ze(E) fluids of the invention.
  • the use of minor quantities of R-161 in place of R-125 allows further improvement of the energy efficiency (COP), further reduction of the GWP of the refrigerant, reduction in condenser operating pressure and reduction in the amount of R-32 required to give comparable cooling capacity.
  • the fluids therefore offer similar performance benefits as already stated. These fluids are especially attractive in applications and equipment where mild f!ammability of the refrigerant can be accepted.
  • the Coefficient of Performance (COP) of the fluids is higher than that of R- 407A in the equivalent cycle conditions.
  • the use of minor quantities of R-161 allows improvement of the energy efficiency (COP) and reduction of the GWP of the refrigerant.
  • a reduction in condenser operating pressure and pressure ratio is also observed, alongside a reduction in the amount of R-32 required to give comparable cooling capacity.
  • the fluids therefore offer similar performance benefits as previously stated. These fluids are especially attractive in applications equipment where mild flammability of the refrigerant can be accepted.
  • Table 3 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 10 % R-12 and 16 % R-134a
  • Table 5 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 10 % R-12 and 20 % R-134a
  • Table 7 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 10 % R-12 and 24 % R-134a
  • Table 8 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 30-40 % R-32, 10 % R-12 and 24 % R-134a
  • Table 9 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 10 % R-12 and 28 % R-134a
  • Table 10 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 10 % R-12 and 28 % R- 34a
  • Table 11 Theoretical Performance Data of Selected R-32/R- 25/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 15 % R-12 and 16 % R- 34a
  • Table 12 Theoretical Performance Data of Selected R-32/R-12S/R-134a/R-1234ze(E) blends containing 30-40 % R-32, 15 % R-12 and 16 % R-134a
  • Table 13 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 15 % R-12 and 20 % R-134a
  • Table 14 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 30-40 % R-32, 15 % R-12 and 20 % R-134a
  • Table 15 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 15 % R-125 and 24 % R- 34a
  • Table 16 Theoretical Performance Data of Selected R-32/R- 25/R-134a/R-1234ze(E) blends containing 30-40 % R-32, 15 % R-125 and 24 % R-134a
  • Table 17 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 15 % R-12 and 28 % -134a
  • Table 18 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 30-40 % R-32, 15 % R-12 and 28 % R-134a
  • Table 19 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 20 % R-12 and 16 % R- 34a
  • Table 20 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 30-40 % R-32, 20 % R-12 and 16 % R-134a
  • Table 21 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 20 % R-12 and 20 % R-134a
  • Table 22 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 30-40 % R-32, 20 % R-12 and 20 % R-134a
  • Table 23 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 20 % R-12 and 24 % R-134a
  • Table 24 Theoretical Performance Data of Selected R-32/R- 25/R-134a/R- 234ze(E) blends containing 30-40 % R-32, 20 % R-12 and 24 % R-134a
  • Table 25 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 20 % R-12 and 28 % R-134a
  • Table 26 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 30-40 % R-32, 20 % R-12 and 28 % R-134a
  • Table 27 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 24 % R-12 and 16 % R- 34a
  • Table 28 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 30-40 % R-32, 24 % R-12 and 16 % R-134a
  • Table 29 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 24 % R-12 and 20 % R-134a
  • Table 30 Theoretical Performance Data of Selected R-32/R-12S/R-134a/R- 234ze(E) blends containing 30-40 % R-32, 24 % R-12 and 20 % R-134a
  • Table 31 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 24 % R-12 and 24 % R- 34a
  • Table 32 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 30-40 % R-32, 24 % R-12 and 24 % R-134a
  • Table 33 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 16-28 % R-32, 24 % R-12 and 28 % R- 34a
  • TabJe 34 Theoretical Performance Data of Selected R-32/R-125/R-134a/R-1234ze(E) blends containing 30-40 % R-32, 24 % R-12 and 28 % R-134a
  • Table 35 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 20 % R-32, 10-20 % R-161 and 0 % R-134a
  • Table 36 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 20 % R-32, 22-32 % R-161 and 10 % R-134a
  • Table 37 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 20 % R-32, 34-46 % R-16 and 10 % R-134a
  • Table 38 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 20 % R-32, 48-60 % R-16 and 10 % R-134a
  • Table 39 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 24 % R-32, 10-20 % R-16 and 10 % R-134a
  • Table 40 Theoretical Performance Data of Selected R-32/R-16 /R-134a/R-1234ze(E) blends containing 24 % R-32, 22-32 % R-16 and 10 % R-134a
  • Table 41 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 24 % R-32, 34-44 % R-16 and 10 % R-134a
  • Table 42 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 24 % R-32, 46-56 % R-16 and 10 % R-134a
  • Table 43 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 28 % R-32, 10-22 % R-16 and 10 % R-134a
  • Table 44 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 28 % R-32, 24-36 % R-16 and 10 % R-134a
  • Table 45 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 28 % R-32, 38-52 % R-16 and 10 % R-134a
  • Table 46 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 30 % R-32, 10-22 % R-16 and 10 % R-134a
  • Table 47 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 30 % R-32, 24-36 % R-161 and 10 % R-134a
  • Table 48 Theoretical Performance Data of Selected R-32/R-16 /R-134a/R-1234ze(E) blends containing 30 % R-32, 38-50 % R-161 and 10 % R-134a
  • Table 49 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 34 % R-32, 10-22 % R-16 and 10 % R-134a
  • Table 50 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 34 % R-32, 24-34 % R-16 and 10 % R-134a
  • Table 51 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 34 % R-32, 36-46 % R-161 and 10 % R-134a
  • Table 52 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 38 % R-32, 10-20 % R-161 and 10 % R-134a
  • Table 53 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 38 % R-32, 22-32 % R-16 and 10 % R-134a
  • Table 54 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 38 % R-32, 34-42 % R-16 and 10 % R-134a
  • Table 55 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 42 % R-32, 10-24 % R-161 and 10 % R-134a
  • Table 56 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 42 % R-32, 26-38 % R-16 and 0 % R-134a
  • Table 57 Theoretical Performance Data of Selected R-32/R-16 /R-134a/R-1234ze(E) blends containing 46 % R-32, 10-22 % R-16 and10%R-134a
  • Table 58 Theoreticai Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 46 % R-32, 24-34 % R-16 and 10%R-134a
  • Table 59 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 20 % R-32, 10-20 % R-16 and 14 % R-134a
  • Table 60 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R- 234ze(E) blends containing 20 % R-32, 22-32 % R-16 and 14 % R-134a
  • Table 61 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 20 % R-32, 34-44 % R-16 and 14 % R-134a
  • Table 62 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 20 % R-32, 46-56 % R-16 and 14 % R-134a
  • Table 63 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 24 % R-32, 10-24 % R-16 and 14 % R-134a
  • Table 64 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 24 % R-32, 26-38 % R-16 and 14 % R-134a
  • Table 65 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 24 % R-32, 26-38 % R-161 and 14 % R- 34a
  • Table 66 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 28 % R-32, 10-22 % R-161 and 14 % R-134a
  • Table 67 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 28 % R-32, 24-36 % R-16 and 14 % R-134a
  • Table 68 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 28 % R-32, 38-50 % R-16 and 14 % R-134a
  • Table 69 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 32 % R-32, 10-22 % R-16 and 14 % R-134a
  • Table 70 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 32 % R-32, 24-34 % R-16 and 14 % R-134a
  • Table 71 Theoretical Performance Data of Selected R-32/R- 61/R-134a/R-1234ze(E) blends containing 32 % R-32, 36-46 % R-16 and14%R-134a
  • Table 72 Theoretical Performance Data of Selected R-32/R-16 /R-134a/R-1234ze(E) blends containing 36 % R-32, 10-20 % R-16 and 4%R- 34a
  • Table 73 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 36 % R-32, 22-32 % R-16 and 14 % R-134a
  • Table 74 Theoretical Performance Data of Selected R-32/R-16 /R-134a/R-1234ze(E) blends containing 36 % R-32, 34-42 % R-16 and 14 % R-134a
  • Table 75 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 40 % R-32, 10-24 % R-16 and 14 % R-134a
  • Table 76 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 40 % R-32, 26-38 % R-16 and 14 % R-134a
  • Table 77 Theoretical Performance Data of Selected R-32/R-16l/F 34a/R-1234ze(E) blends containing 44 % R-32, 10-22 % R-16 and 14 % R-134a
  • Table 78 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 44 % R-32, 24-34 % R-16 and 14 % R-134a
  • Table 79 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze ⁇ E) blends containing 20 % R-32, 10-24 % R-16 and 18 % R-134a
  • Table 80 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 20 % R-32, 26-40 % R-16 and 18 % R-134a
  • Table 81 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 20 % R-32, 42-54 % R-16 and 18 % R-134a
  • Table 82 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 24 % R-32, 10-22 % R-16 and 18 % R-134a
  • Table 83 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 24 % R-32, 24-36 % R-16 and 18 % R- 34a
  • Table 84 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 24 % R-32, 38-50 % R-16 and 18 % R-134a
  • Table 85 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 28 % R-32, 10-20 % R-16 and 18%R-134a
  • Table 86 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 28 % R-32, 22-32 % R-16 and 8%R-134a
  • Table 87 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 28 % R-32, 34-46 % R-161 and 18 % R- 34a
  • Table 88 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 32 % R-32, 10-20 % R-161 and 18 % R-134a
  • Table 89 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 32 % R-32, 22-32 % R-16 and 18 % R-134a
  • Table 90 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 32 % R-32, 34-42 % R-16 and 18 % R-134a
  • Table 91 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 36 % R-32, 10-22 % R-161 and 18 % R-134a
  • Table 92 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 36 % R-32, 24-38 % R-161 and 18 % R-134a
  • Table 93 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 40 % R-32, 10-20 % R-161 and 18 % R-134a
  • Table 94 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 40 % R-32, 22-34 % R-161 and 18 % R-134a
  • Table 95 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 20 % R-32, 10-22 % R-16 and 22 % -134a
  • Table 96 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 20 % R-32, 24-36% R-16 and 22 % R-134a
  • Table 97 Theoretical Performance Data of Selected R-32/R-16 /R-134a/R-1234ze(E) blends containing 20 % R-32, 38-48 % R-16 and 22 % R-134a
  • Table 98 Theoretical Performance Data of Selected R-32/R-16l/R-134a/R-1234ze(E) blends containing 24 % R-32, 10-20 % R-16 and 22 % R-134a
  • Table 99 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 24 % R-32, 22-32 % R-16 and 22 % R-134a
  • Table 100 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 24 % R-32, 34-46 % R-16
  • Table 101 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 28 % R-32, 10-24 % R-161 and 22 % R- 34a
  • Table 102 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 28 % R-32, 26-40 % R-161 and 22 % R-134a
  • Table 102 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 32 % R-32, 10-22 % R-16 and 22 % R-134a
  • Table 103 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 32 % R-32, 24-36 % R-16 and 22 % R-134a
  • Table 104 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 36 % R-32, 10-20 % R-161 and 22 % R-134a
  • Table 105 Theoretical Performance Data of Selected R-32/R-161/R-134a/R-1234ze(E) blends containing 36 % R-32, 22-32 % R-16 and 22 % R-134a
  • Table 106 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 10 % R-12 and 10 % R-161
  • Table 107 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 10 % R-12 and 15 % R-161
  • Table 108 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 10 % R-125 and 20 % R-161
  • Table 109 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 10 % R-125 and 25 % R-161
  • Table 110 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 10 % R-125 and 30 % R-161
  • Table 111 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 15 % R-125 and 10 % R-161
  • Table 112 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 15 % R-12 and 5 % R- 61
  • Table 113 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 15 % R-12 and 20 % R-161
  • Table 114 Theoretical Performance Data of Selected R-32/R-l25/R-161/R-1234ze(E) blends containing 16-40 % R-32, 15 % R-125 and 25 % R-161
  • Table 115 Theoretical Performance Data of Selected R-32/R-l25/R-161/R-1234ze(E) blends containing 16-40 % R-32, 15 % R-125 and 30 % R-161
  • Table 116 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 20 % R-12 and 10 % R-161
  • Table 117 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 20 % R-12 and 15 % R-161
  • Table 118 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 20 % R-12 and 20 % R-161
  • Table 119 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 20 % R-12 and 25 % R-161
  • Table 120 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 20 % R-12 and 30 % R-161
  • Table 121 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 25 % R-12 and 10 % R-161
  • Table 122 Theoretical Performance Data of Selected R-32/R- 25/R-161/R-1234ze(E) blends containing 16-40 % R-32, 25 % R-12 and 15 % R-161
  • Table 123 Theoretical Performance Data of Selected R-32/R-l25/R-161/R-1234ze(E) blends containing 16-40 % R-32, 25 % R-12 and 20 % R-161
  • Table 124 Theoretical Performance Data of Selected R-32/R-125/R-161/R-1234ze(E) blends containing 16-40 % R-32, 25 % R-12 and 25 % R-161

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Abstract

L'invention concerne une composition de transfert thermique comprenant : (i) du trans-1,3,3,3-tétrafluoropropène (R-1234ze(E)) ; (ii) un deuxième composant choisi parmi le difluorométhane (R-32), le propène (R-1270), le propane (R290) et des mélanges de ceux-ci ; (iii) un troisième composant choisi parmi le pentafluoroéthane (R-125), le 1,1,1,2-tétrafluoroéthane (R-134a), et des mélanges de ceux-ci ; et facultativement (iv) un quatrième composant choisi parmi le fluoroéthane (R-161), le 1,1-difluoroéthane (R-152a) et des mélanges de ceux-ci.
PCT/GB2011/000952 2010-06-25 2011-06-24 Compositions de transfert thermique Ceased WO2011161419A1 (fr)

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EP11738255.6A EP2609168B1 (fr) 2010-06-25 2011-06-24 Compositions de transfert thermique
BR112012030454A BR112012030454A2 (pt) 2010-06-25 2011-06-24 composição de transferência de calor, dispositivos de transferência de calor e de geração de energia mecânica, uso da composição, agente de expensão , composição para formação de espuma, espuma, composição borrifável, métodos para esfriar um artigo, para aquecer um artigo, para extrair uma substância de biomassa, para limpar um artigo, para extrair um material de uma solução aquosa, para extrair um material de uma matriz sólida particulada, para reduzir o impacto ambiental decorrente da operação de um produto, para preparar a composição, para gerar crédito de emissão de gás de efeito estufa
EP23192441.6A EP4253501A3 (fr) 2010-06-25 2011-06-24 Compositions de transfert de chaleur
ES11738255.6T ES2545186T3 (es) 2010-06-25 2011-06-24 Composiciones de transferencia de calor
RU2013103360/05A RU2567950C2 (ru) 2010-06-25 2011-06-24 Композиция теплоносителя
EP15169704.2A EP2930222B1 (fr) 2010-06-25 2011-06-24 Compositions de transfert de chaleur
CA2800762A CA2800762A1 (fr) 2010-06-25 2011-06-24 Compositions de transfert thermique
AU2011268772A AU2011268772B2 (en) 2010-06-25 2011-06-24 Heat transfer compositions
CN2011800309611A CN102959036A (zh) 2010-06-25 2011-06-24 传热组合物
KR1020137002172A KR101349716B1 (ko) 2010-06-25 2011-06-24 열전달 조성물
PL11738255T PL2609168T3 (pl) 2010-06-25 2011-06-24 Kompozycje do wymiany ciepła
US13/701,328 US20130193369A1 (en) 2010-06-25 2011-06-24 Heat transfer compositions
MX2012013767A MX2012013767A (es) 2010-06-25 2011-06-24 Composiciones de transferencia de calor.
US14/851,030 US10266736B2 (en) 2010-06-25 2015-09-11 Heat transfer compositions
US16/391,554 US10844260B2 (en) 2010-06-25 2019-04-23 Heat transfer compositions
US17/094,434 US11760911B2 (en) 2010-06-25 2020-11-10 Heat transfer compositions
US18/456,665 US20230416582A1 (en) 2010-06-25 2023-08-28 Heat transfer compositions

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CN (1) CN102959036A (fr)
AU (1) AU2011268772B2 (fr)
BR (1) BR112012030454A2 (fr)
CA (1) CA2800762A1 (fr)
DK (1) DK2930222T3 (fr)
ES (2) ES2545186T3 (fr)
GB (1) GB2481443B (fr)
HK (1) HK1215041A1 (fr)
MX (1) MX2012013767A (fr)
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